Liquid cleaning agent composition for hard surfaces

Abstract

To provide a liquid detergent composition for a hard surface having excellent stability of a cleaning composition system, which provides sufficient cleaning properties for starch stains, oil stains and protein stains and re-adhesion prevention properties even when the hardness of water used for cleaning is high.SOLUTION: There is provided a liquid detergent composition for a hard surface which comprises (A) an alkanolamine, (B) a polyelectrolyte polymer, (C) a nonionic surfactant, (D) an enzyme, (E) a solubilizer and (F) water, wherein the polyelectrolyte polymer (B) contains the following (B1) and (B2) and the mass ratio (B1 / B2) of (B1) to (B2) is set to 0.1 to 6. (B1) 0.5 to 5 mass% of a polyelectrolyte polymer having a pH of 4 or less at 25°C and a mass average molecular weight of 1000 to 500000 which has a carboxy group, (B2) 0.5 to 5 mass% of a potassium salt and / or a sodium salt of a polyelectrolyte polymer having a mass average molecular weight of 1000 to 100000 which has a carboxy group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid detergent composition for hard surfaces, and more particularly to a liquid detergent composition for hard surfaces used when washing hard surfaces such as dishes, various containers, and utensils with an automatic dishwasher.

[0002] Conventionally, in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, etc., automatic dishwashers are widely used to efficiently wash used dishes. Also, not limited to dishes, in various manufacturing factories, processing factories, etc., various automatic washers are used to wash utensils, containers, plastic containers used in distribution, etc. Furthermore, in general households, automatic washers have been rapidly spreading in recent years.

[0003] For this reason, various detergent compositions have been proposed as detergent compositions for use in automatic washers for hard surface cleaning. For example, in Patent Document 1, a detergent composition excellent in detergency and foam breakage is proposed, which prepares three types of nonionic surfactants and contains alkanolamine and an enzyme. Also, in Patent Document 2, a detergent composition that effectively acts on strongly adhering starch stains and enhances detergency is proposed, which contains α - amylase and alkaline protease. And in Patent Document 3, a detergent composition that prevents coloring of tea stain and enhances detergency against tea stain and other stains even when the stock solution is weakly alkaline is proposed, which contains a low - molecular chelating agent, a copolymer of acrylic acid and maleic acid, and an alkanolamine compound. Furthermore, in Patent Document 4, a detergent composition for removing accumulated stains is proposed, which contains polyacrylic acid (salt), maleic acid (salt) - acrylic acid (salt) copolymer, and maleic acid (salt) - olefin copolymer.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

[0005] However, the invention described in Patent Document 1 has the problem that sufficient cleaning performance cannot be obtained when the hardness of the water used for cleaning is high. Also, there is no mention of the re-adhesion of dirt, which affects the finish. Although the invention described in Patent Document 2 has evidence of cleaning performance on soiled cloths, there are no examples on hard surfaces, and therefore no evidence of cleaning performance on hard surfaces. Also, this invention improves the cleaning performance against starch stains, and there is no mention of cleaning performance or re-adhesion prevention for other stains (e.g., oil stains, protein stains). The invention described in Patent Document 3 may worsen tea stains or cause scale formation if the hardness of the water used for cleaning is high. Also, there is no mention of cleaning performance against stains other than tea stains. Although the invention described in Patent Document 4 shows cleaning performance by combining each component, if the cleaning composition is in liquid form, there is a risk of problems with the stability of the system, so only a solid-forming type is disclosed.

[0006] Therefore, against this background, the present invention aims to provide a liquid cleaning agent composition for hard surfaces that provides sufficient cleaning performance and re-adhesion prevention against starch stains, oil stains, and protein stains, even when the hardness of the water used for cleaning is high, and that exhibits excellent stability of the cleaning composition system. [Means for solving the problem]

[0007] However, in view of these circumstances, the inventors conducted extensive research and, as a result, discovered that by using two types of polymer electrolyte polymers, an acid and a salt, in combination in a weakly alkaline liquid cleaning agent composition for hard surfaces, it is possible to stably incorporate polymer electrolyte polymers with a molecular weight of 10,000 or more, which had previously been difficult to include stably in liquid cleaning agent compositions. Furthermore, it is possible to improve the cleaning performance and re-adhesion prevention of starch stains, oil stains, and protein stains without including a chelating agent, thus completing the present invention.

[0008] In other words, the present invention has the following embodiments [1] to [4]. [1] A liquid cleaning agent composition for hard surfaces comprising (A) an alkanolamine, (B) a polyelectrolyte polymer, (C) a nonionic surfactant, (D) an enzyme, (E) a solubilizer, and (F) water, wherein the (B) polyelectrolyte polymer contains the following (B1) and (B2), the content of (B1) and (B2) is set to the following ranges with respect to the entire liquid cleaning agent composition for hard surfaces, and the mass ratio of (B1) to (B2) (B1 / B2) is set to 0.1 to 6. (B1) A polyelectrolyte polymer having a carboxyl group and a mass-average molecular weight of 1,000 to 500,000, with a pH of 4 or less at 25°C: 0.5 to 5% by mass. (B2) Potassium salts and / or sodium salts of polyelectrolyte polymers having a carboxyl group and a mass-average molecular weight of 1,000 to 1,000,000: 0.5 to 5% by mass. [2] The liquid cleaning agent composition for hard surfaces according to [1], wherein the (C) nonionic surfactant has at least one selected from the group consisting of (C1), (C2), and (C3) below, and the content of (C1), (C2), and (C3) is set to the following ranges with respect to the entire liquid cleaning agent composition for hard surfaces, and the sum of (C1), (C2), and (C3) is 1 to 10% by mass of the entire liquid cleaning agent composition for hard surfaces. (C1) A nonionic surfactant consisting of a polyoxyalkylene alkyl ether, having a cloud point of 35°C or less in a 1% by mass aqueous solution: 5% by mass or less. (C2) A nonionic surfactant consisting of a mixture of polyoxyalkylene alkyl ether and polyalkylene glycol, having a cloud point of 35°C or less in a 1% by mass aqueous solution: 5% by mass or less. (C3) A nonionic surfactant consisting of polyoxyethylene polyoxypropylene decyl ether, having a cloud point of 35°C or less in a 1% by mass aqueous solution: 10% by mass or less. [3] A liquid cleaning agent composition for hard surfaces according to [1] or [2], wherein the pH at 25°C is set in the range of 8.0 to 10.0. [4] Does not contain chelating agents, or if it does, the amount is 1% by mass or less. [1] A liquid cleaning agent composition for hard surfaces as described in any of the following [3]. [Effects of the Invention]

[0009] The present invention contains (A) an alkanolamine, (B) a polyelectrolyte polymer, (C) a nonionic surfactant, (D) an enzyme, (E) a solubilizer, and (F) water. Since the (B) polyelectrolyte polymer contains two types of polyelectrolyte polymers, a specific acid and a salt, storage stability is ensured even when a salt of the (B) polyelectrolyte polymer with a molecular weight of 10,000 or more is included. Moreover, because the two types of polyelectrolyte polymers are used in a predetermined ratio, the cleaning performance and re-adhesion prevention performance of different types of stains, such as starch stains, oil stains, and protein stains, can be improved without the inclusion of a chelating agent. Therefore, the present invention offers excellent cleaning performance against various types of dirt in a wide range of applications, such as detergents for automatic dishwashers, pre-wash detergents, and direct-spray detergents. It also exhibits excellent storage stability, enzyme activity stability, low foaming, and re-adhesion prevention, making it highly versatile and easy to use. [Modes for carrying out the invention]

[0010] The present invention will be described below based on examples of embodiments for carrying out the present invention. However, the present invention is not limited to the embodiments described below. In the present invention, when expressed as "X to Y" (X and Y are arbitrary numbers), unless otherwise specified, it means "X or more and Y or less", and also includes the meaning of "preferably greater than X" or "preferably less than Y". When expressed as "X or more" (X is an arbitrary number) or "Y or less" (Y is an arbitrary number), it also includes the meaning of "preferably greater than X" or "preferably less than Y". Furthermore, "X and / or Y (X and Y are arbitrary components)" means at least one of X and Y, and includes three cases: only X, only Y, and X and Y.

[0011] The liquid detergent composition for hard surfaces according to one embodiment of the present invention (hereinafter sometimes referred to as the "detergent composition") is a liquid detergent composition for hard surfaces containing (A) alkanolamine, (B) polyelectrolyte polymer, (C) nonionic surfactant, (D) enzyme, (E) solubilizer, and (F) water. The above-mentioned (B) polyelectrolyte polymer contains the following (B1) and (B2), and the contents of (B1) and (B2) are set within the following ranges with respect to the entire liquid detergent composition for hard surfaces, and the mass ratio of (B1) to (B2) (B1 / B2) is set to 0.1 to 6. (B1) A polyelectrolyte polymer having a carboxy group and a mass average molecular weight of 1000 to 500000, with a pH of 4 or less at 25°C. (B2) Potassium salt and / or sodium salt of a polyelectrolyte polymer having a carboxy group and a mass average molecular weight of 1000 to 100000. Hereinafter, each component will be described.

[0012] <Component A: Alkanolamine> As the alkanolamine used as the component (A) of the present invention, for example, a compound having a hydroxy group and an amino group in an alkane skeleton can be used. Examples of such compounds include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N - ethyldiethanolamine, N - ethylethanolamine, N - methyldiethanolamine, and N - methylethanolamine. Among them, triethanolamine, diethanolamine, monoethanolamine, monoisopropanolamine, N - ethyldiethanolamine, N - methyldiethanolamine, and N - methylethanolamine are preferably used. More preferably, they are triethanolamine, diethanolamine, and monoethanolamine. These can be used alone or in combination of two or more.

[0013] The content of the above component (A) is not particularly limited. For example, it is preferably set within the range of 10 - 30% by mass, more preferably within the range of 12 - 25% by mass, and even more preferably within the range of 15 - 22% by mass with respect to the total amount of the detergent composition. That is, if the content of component (A) is too low, the detergency of protein stains tends to be poor. On the contrary, if the content of component (A) is too high, the rinsability when used in a dishwashing machine deteriorates, the balance of each performance of the detergent composition worsens, it becomes difficult to obtain a synergistic effect with other components, and there is also a tendency to be disadvantageous in terms of cost.

[0014] <Component (B): Polyelectrolyte polymer> The polyelectrolyte polymer used as component (B) of the present invention contains the following (B1) and (B2) in specific amounts respectively, and the mass ratio (B1 / B2) of (B1) to (B2) is set to 0.1 - 6. Therefore, even when using a salt of a polyelectrolyte polymer with a molecular weight of 10,000 or more in the present invention, it can be used in combination with component (A) to achieve the stability of the system. (B1) A polyelectrolyte polymer having a carboxy group with a mass average molecular weight of 1000 - 500000 and a pH of 4 or less at 25°C. (B2) A potassium salt and / or a sodium salt of a polyelectrolyte polymer having a carboxy group and a mass average molecular weight of 1,000 to 100,000. In the present invention, the "polyelectrolyte polymer" means a polymer having a molecular weight of several thousand to several hundred thousand, having a dissociating group in the polymer chain, and dissociating in water to become a polymer ion.

[0015] Examples of the component (B1) include acrylic acid polymers, maleic acid polymers, acrylic acid-maleic acid copolymers, poly-α-hydroxyacrylic acid, acrylic acid-maleic acid-polyethylene glycol copolymers, olefin-maleic acid copolymers, acrylic acid-sulfonic acid copolymers, etc. Maleic acid polymers, acrylic acid-maleic acid copolymers, and polyacrylic acid are more preferably used. These can be used alone or in combination of two or more. As described above, the mass average molecular weight of the component (B1) is 1,000 to 500,000, but from the viewpoint of increasing the viscosity of the detergent composition, it is preferably 1,500 to 250,000, and more preferably 1,800 to 150,000. The content of the component (B1) is set within the range of 0.5 to 5% by mass based on the total mass of the detergent composition from the viewpoints of the decrease in pH and the storage stability of the entire detergent composition, and it is preferably set within the range of 1 to 3% by mass.

[0016] The component (B1) is usually used as an aqueous solution, and the pH in the existing state is 4 or less at a temperature of 25°C, preferably pH 1.0 to 4.0, and more preferably pH 1.5 to 3.5.

[0017] Examples of (B2) above include salts of acrylic acid polymers, salts of maleic acid polymers, salts of acrylic acid-maleic acid copolymers, salts of poly-α-hydroxyacrylic acid, salts of acrylic acid-maleic acid-polyethylene glycol copolymers, salts of olefin-maleic acid copolymers, and salts of acrylic acid-sulfonic acid copolymers. Furthermore, examples of these salts include sodium salts, potassium salts, ammonium salts, and ethanolamine salts, with sodium polyacrylate, sodium acrylic acid-sulfonic acid copolymers, sodium acrylic acid-maleic acid copolymers, and sodium olefin-maleic acid copolymers being more preferably used. These can be used individually or in combination of two or more. The mass-average molecular weight of (B2) above is 1,000 to 100,000 as described above, but from the viewpoint of compositional balance of the detergent composition, it is preferably 1,500 to 60,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 20,000. The content of component (B2) described above should be set within the range of 0.5 to 5% by mass relative to the total mass of the detergent composition, and preferably within the range of 1 to 3% by mass, from the viewpoint of storage stability of the detergent composition as a whole.

[0018] The mass ratio (B1 / B2) of (B1) to (B2) is set to 0.1 to 6 as described above, but is preferably set to the range of 0.2 to 4, and more preferably to the range of 0.6 to 3. If the above mass ratio (B1 / B2) is too low, the overall balance will be poor and storage stability will tend to decrease, while if it is too high, the overall pH will decrease and it will be difficult to obtain the desired washing performance.

[0019] Although the content of the above component (B) is not particularly limited, it is preferably in the range of 1 to 5.5% by mass, more preferably 1 to 3% by mass, based on the total detergent composition. That is, if the content of the polyelectrolyte polymer is too low, it tends to be difficult to obtain the desired anti-redeposition effect, detergency, and scale formation inhibitory effect. Also, if the content of the polyelectrolyte polymer is too high, the overall balance deteriorates, the storage stability decreases, and the synergistic effect with other components tends not to be obtained further. The above component (B) can also be used for pH adjustment. In particular, it is preferable that the total mass of (B1) and (B2) is set within the range of 70 to 100% by mass, more preferably within the range of 85 to 100% by mass, and even more preferably 100% by mass, based on the total mass of component (B). That is, when the total mass of (B1) and (B2) is set within the above range, it tends to be more excellent in the ability to sequester metal ions, the threshold effect, the dispersibility of water-insoluble substances, the anti-redeposition effect of dirt, and detergency in the balance with other components.

[0020] <Component C: Nonionic surfactant> The nonionic surfactant used as the component (C) of the present invention preferably contains at least one selected from the group consisting of the following (C1), (C2), and (C3). (C1) A nonionic surfactant composed of a polyoxyalkylene alkyl ether having a cloud point of 35°C or lower in a 1% by mass aqueous solution. (C2) A nonionic surfactant composed of a mixture of a polyoxyalkylene alkyl ether and a polyalkylene glycol having a cloud point of 35°C or lower in a 1% by mass aqueous solution. (C3) A nonionic surfactant composed of a polyoxyethylene polyoxypropylene decyl ether having a cloud point of 35°C or lower in a 1% by mass aqueous solution.

[0021] Examples of (C1) above include polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxybutylene alkyl ether, and polyoxyethylene polyoxypropylene polyoxybutylene alkyl ether, which have a cloud point of 35°C or lower when used as a 1% by mass aqueous solution. These can be used individually or in combination of two or more. Furthermore, the addition polymerization of the polyoxyalkylene may be a random or block copolymer of two or three monomers. The number of carbon atoms in the alkyl group of the polyoxyalkylene alkyl ether is preferably 8 to 22, more preferably 10 to 20, and even more preferably 12 to 18. It is believed that using these surfactants as (C1) in amounts below a certain level will enhance cleaning and anti-foaming properties. The content of (C1) is preferably set to 5% by mass or less of the total cleaning agent composition.

[0022] The polyoxyalkylene alkyl ether used in (C2) above is a polyoxyethylene-polyoxypropylene alkyl ether obtained by adding 1 to 40 moles of ethylene oxide (hereinafter "ethylene oxide" is abbreviated as "EO") and 1 to 50 moles of propylene oxide (hereinafter "propylene oxide" is abbreviated as "PO") to a linear or branched alcohol having 6 to 24 carbon atoms in the alkyl group. For example, it is preferable to use a linear or branched alcohol having 6 to 18 carbon atoms to which 1 to 20 moles of EO and 1 to 20 moles of PO are added, resulting in an EO / PO weight ratio in the range of 0.5 to 5, or a linear or branched alcohol having 6 to 18 carbon atoms to which 1 to 15 moles of EO and 1 to 50 moles of PO are added, resulting in an EO / PO weight ratio in the range of 0.05 to 1. Furthermore, the polyalkylene glycol mixed with the polyoxyalkylene alkyl ether is a polymer in which hydrocarbons are linked by ether bonds, and examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These can be used individually or in combination of two or more. They may also be random or block copolymers of two or more of these. The molecular weight of the polyalkylene glycol is not particularly limited, but from the viewpoint of dispersion uniformity, those with a molecular weight of 500 to 100,000 are preferably used. The content of (C2) described above is preferably set to 5% by mass or less of the total detergent composition.

[0023] The above (C3) is a polyoxyethylene polyoxypropylene decyl ether whose 1% by mass aqueous solution has a cloud point of 35°C or lower, and among these, polyoxyalkylene branched decyl ether is more preferably used in terms of low foaming properties. The content of the above (C3) is preferably set to 10% by mass or less of the total detergent composition.

[0024] The above (C1), (C2), and (C3) all use a 1% by mass aqueous solution with a cloud point of 35°C or lower. In other words, using a nonionic surfactant with a cloud point exceeding 35°C as component (C) in the present invention is advantageous in that it solubilizes other nonionic surfactants in the detergent composition, but it tends to reduce the anti-foaming properties of other nonionic surfactants when used in machines that spray detergent solution for cleaning, such as dishwashers.

[0025] Furthermore, in the present invention, the total mass of (C1), (C2), and (C3) is usually set to 1 to 10% by mass of the entire detergent composition, preferably 1.5 to 7% by mass, and more preferably 2 to 5% by mass. In other words, when the total mass of (C1), (C2), and (C3) is set within the above range, there is a tendency for the cleaning properties and re-adhesion prevention properties, especially for oils and fats, to be higher. In addition, if the total mass of (C1), (C2) and (C3) is too large, not only the overall balance tends to deteriorate, but also the synergistic cleaning performance with other components becomes saturated and it tends to be disadvantageous in terms of cost. Conversely, if it is too small, the foam suppression property and solubilization ability tend not to be fully exhibited.

[0026] The mass ratio (C2 / C1) of (C2) to (C1) is preferably set to 1.5 to 5, more preferably 2 to 4, from the viewpoint of detergency. Also, the mass ratio (C2 / C3) of (C2) to (C3) is preferably set to 1.5 to 5, more preferably 2 to 4, from the viewpoint of foam suppression property.

[0027] <Component (D): Enzyme> As the enzyme which is the component (D) of the present invention, various enzymes for detergents can be used. Examples of such enzymes include amylase, protease, lipase, cellulase, and glucanase. These enzymes may be used alone or in combination of two or more. The component (D) is used to obtain a cleaning effect on specific stains that are difficult to compensate for with other detergent components by its enzyme activity. From the viewpoints of cleaning effect and cost, α - amylase, protease, and lipase are preferably used.

[0028] The content of the component (D) is not particularly limited, but is preferably in the range of 0.1 to 7% by mass, more preferably 0.5 to 5% by mass, based on the total detergent composition. That is, when the content of the component (D) is set within the above range, the decomposability of various stains such as starch, oil and fat, and protein becomes high, and the tendency to prevent redeposition also becomes high. In addition, if the content of the component (D) is too small, the improvement in detergency becomes poor due to the balance with other components. Conversely, if the content of the component (D) is too large, not only is it difficult to obtain a synergistic effect with other components, but it is also disadvantageous in terms of cost.

[0029] <Component (E): Solubilizer> The solubilizer, which is the component (E) of the present invention, is used for the purpose of stably solubilizing the nonionic surfactant which is the component (C), and examples thereof include aromatic sulfonates and alkyl polyglucosides. In particular, cumene sulfonate, xylene sulfonate, paratoluenesulfonate, and alkyl polyglucosides containing an alkyl residue having 6 to 16 carbon atoms are preferably used because of their excellent solubilizing power and high storage stability in a wide temperature range. Sodium cumene sulfonate, hexyl glucoside, and decyl glucoside are more preferable. These can be used alone or in combination of two or more. Although the content of the above-mentioned component (E) is not particularly limited, for example, it is preferably set within the range of 5 to 25% by mass, more preferably within the range of 7 to 22% by mass, and even more preferably within the range of 10 to 20% by mass with respect to the whole of this detergent composition. That is, when the content of the component (E) is set within the above range, the stability of the system tends to be higher. This is because when the content of the component (E) is too small, the amount capable of solubilizing the component (C) tends to be small, and conversely, when the content of the component (E) is too large, the solubilizing ability becomes saturated, which tends to be disadvantageous in terms of cost.

[0030] <Component F: Water> Examples of the water as the component (F) of the present invention include pure water, ion-exchanged water, soft water, distilled water, tap water, and the like. These can be used alone or in combination of two or more. In addition, the above-mentioned "water" is the sum of the water contained in the form of crystal water or aqueous solution derived from each component constituting the detergent composition and the water added from the outside, and is contained as a balance so that the whole detergent composition becomes 100% by mass.

[0031] The detergent composition of the present invention is prepared using the above components (A) to (F) as essential components, and can further appropriately contain various optional components. Examples of such optional components include water-soluble solvents, enzyme stabilizers, neutralizing components, preservatives, fragrances, thickeners, bactericides, and the like. These can be used alone or in combination of two or more.

[0032] However, since the pH of the present invention can be adjusted with alkanolamines, a pH adjuster is usually not necessary. In other words, from the standpoint of reducing storage stability and being costly, it is preferable not to include a pH adjuster. Even if a pH adjuster is included, it is preferable that it be 1% by mass or less of the total detergent composition, more preferably 0.5% by mass or less, and even more preferably not included at all.

[0033] Furthermore, the present invention exhibits resistance to the re-adhesion of oil and protein stains even without containing a chelating agent, therefore, it does not need to contain a chelating agent. In other words, from the standpoint of reducing storage stability and environmental risks from wastewater, it is preferable not to include a chelating agent. Even if a chelating agent is included, it is preferable that it be 1% by mass or less of the total detergent composition, more preferably 0.1% by mass or less, and even more preferably not included at all.

[0034] The detergent composition of the present invention can be prepared using the essential components (A) to (F) and any optional components thereof as needed, according to the usual method for preparing detergent compositions.

[0035] The detergent composition of the present invention obtained in this manner contains (A) an alkanolamine, (B) a polyelectrolyte polymer, (C) a nonionic surfactant, (D) an enzyme, (E) a solubilizer, and (F) water, wherein the (B) polyelectrolyte polymer contains the following (B1) and (B2), the content of (B1) and (B2) is set to the following ranges with respect to the entire liquid detergent composition for hard surfaces, and the mass ratio of (B1) to (B2) (B1 / B2) is set to 0.1 to 6. (B1) A polyelectrolyte polymer having a carboxyl group and a mass-average molecular weight of 1,000 to 500,000, with a pH of 4 or less at 25°C: 0.5 to 5% by mass. (B2) Potassium salts and / or sodium salts of polyelectrolyte polymers having a carboxyl group and a mass-average molecular weight of 1,000 to 1,000,000: 0.5 to 5% by mass.

[0036] The detergent composition of the present invention exhibits cleaning ability, low foaming, and anti-re-adhesion properties regardless of water hardness. Furthermore, even if the liquid detergent composition contains no chelating agent or only a very low amount, the system remains stable, exhibiting excellent storage stability and enzyme activity stability, and exhibiting anti-re-adhesion properties for various types of stains, including starch, oil, and protein stains, making it easy to use.

[0037] In particular, those with a pH set in the range of 8.0 to 10.0 at 25°C are preferred, and more preferably in the range of 8.5 to 9.5. That is, a higher pH can be expected to result in higher cleaning power, but if the pH becomes too high, it tends to have adverse effects on the environment and safety. However, when the pH of the detergent composition of the present invention is set within the above range, high cleaning performance can be achieved while considering the environment and safety. Furthermore, it can prevent corrosion of the objects being cleaned, such as aluminum tableware and cooking utensils, thereby increasing its versatility. In addition, it can ensure the stability of enzyme activity, making it suitable for long-term storage. The pH values ​​above were measured for the undiluted detergent composition before dilution.

[0038] Furthermore, the cleaning agent composition of the present invention is not only suitable for cleaning hard surfaces such as glass, ceramics, metal, and plastic, but can also be used in automatic washing machines for cleaning equipment and containers in various manufacturing and processing plants, as well as plastic containers used in distribution. In addition, it can be preferably used for cleaning hard surfaces such as tiles and floors in food factories and food processing plants, cleaning containers such as glass bottles and beer bottles for beverages, and cleaning metal surfaces. In particular, it can be preferably used in automatic dishwashers in hotels, restaurants, schools, hospitals, eateries, catering companies, and company cafeterias.

[0039] Furthermore, the cleaning agent composition of the present invention can exhibit excellent cleaning performance on objects when supplied, for example, to an automatic cleaning machine as a cleaning agent aqueous solution at a concentration of 0.02 to 0.5% by mass, taking into consideration the type and amount (degree) of dirt. [Examples]

[0040] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0041] [Examples 1-23, Comparative Examples 1-12] Detergent compositions were prepared according to the compositions shown in Tables 1-6 below (the values ​​in each table are expressed as "mass%" in their original state). These compositions were evaluated for the following: cleaning performance in cleaning tests 1 (as a detergent for automatic dishwashers), 2 (as a pre-wash detergent), 3 (when sprayed directly onto dirt), 4 (when the water hardness is high), storage stability, enzyme activity stability, low foaming, and anti-re-adhesion properties. pH (undiluted, 25°C) was also measured. These results are shown in Tables 1-6 below. The testing methods and evaluation criteria for each item are as follows.

[0042] [Washing Test 1] To evaluate the cleaning performance of the detergent as an automatic dishwasher detergent, the following tests and evaluations were conducted. • Test method The prepared detergent composition was placed in a commercial automatic dishwasher (JWE-680UB-G, manufactured by Hoshizaki Corporation) and operated under the following operating conditions. Then, 10 porcelain plates or bowls, as specified below, were washed in sets of 10, and their cleaning performance was evaluated according to the evaluation criteria described later. Three types of stains were prepared for cleaning: starch (porridge), oil (beef tallow), and protein (egg yolk), and an evaluation was conducted for each type of stain. *Driving conditions Detergent concentration: 0.20% Washing temperature: 45℃ Rinse temperature: 80℃ Washing course: Standard washing cycle (Wash: 30 seconds, Rinse: 8 seconds) Hardness of water used: (as CaCO3) 50-60 ppm Starch (porridge) stains: 40g of cooked rice was placed in 400g of hot water, boiled at 90-100°C for 20 minutes, and the supernatant was applied to a bowl so that 0.6g per bowl was covered with the residue. After drying at room temperature for 30 minutes, the bowl was soaked in 40°C water for 10 minutes immediately before washing. Fat (beef tallow) stains: A 25cm diameter porcelain plate was used, with 4g of refined beef tallow applied to each plate. Protein (egg yolk) stains: Egg yolks were applied to 25cm diameter porcelain plates at a rate of 4g per plate. The plates were dried at room temperature for 1 hour, and then immersed in 40°C water for 30 minutes immediately before washing. • Evaluation criteria For starch (porridge) stains, an iodine solution was applied to the bowls after washing; for oil (beef tallow) stains, an oil red solution was applied to the porcelain plates after washing; and for protein (egg yolk) stains, the degree of stain removal was evaluated visually according to the following criteria. ◎: Removes over 90% of dirt. ○: Removes 70% or more of dirt but less than 90%. △: Removes 50% or more but less than 70% of dirt. ×: Removes less than 50% of dirt.

[0043] [Washing Test 2] To evaluate the cleaning performance of the detergent as a pre-washing agent, the following tests and evaluations were conducted. • Test method Five pieces of tableware, similar to those prepared in "Cleaning Test 1," were prepared for each type of stain, and these were immersed in the prepared cleaning solution under the following conditions. Subsequently, the dishes were washed in a commercial automatic dishwasher (JWE-680UB-G, manufactured by Hoshizaki Corporation) without detergent using the following method, and evaluated according to the following evaluation criteria. *Immersion conditions Detergent concentration: 0.10% Soaking temperature: 25℃ Immersion time: 10 minutes * Washing machine operating conditions Washing temperature: 45℃ Rinse temperature: 80℃ Washing course: Standard washing cycle (Wash: 30 seconds, Rinse: 8 seconds) Hardness of water used: (as CaCO3) 50-60 ppm • Evaluation criteria For starch (porridge) stains, an iodine solution was applied to the bowl after washing; for oil (beef tallow) stains, an oil red solution was applied to the porcelain plate after washing; and for protein (egg yolk) stains, the degree of stain removal was evaluated visually as follows. ◎: Removes over 90% of dirt. ○: Removes 70% or more of dirt but less than 90%. △: Removes 50% or more but less than 70% of dirt. ×: Removes less than 50% of dirt.

[0044] [Washing Test 3] To evaluate the cleaning performance when sprayed directly onto dirt, the following tests and evaluations were conducted. • Test method Five dishes, similar to those prepared in "Washing Test 1," were prepared for each type of stain. A 10% by mass aqueous solution of detergent, prepared from a spray bottle, was sprayed evenly onto the prepared stained dishes. After being left at room temperature (around 23°C) for one hour, the dishes were washed in a commercial automatic dishwasher (JWE-680UB-G, manufactured by Hoshizaki Corporation) without detergent under the following conditions and evaluated according to the following evaluation criteria. * Washing machine operating conditions Washing temperature: 45℃ Rinse temperature: 80℃ Washing course: Standard washing cycle (Wash: 30 seconds, Rinse: 8 seconds) Hardness of water used: (as CaCO3) 50-60 ppm • Evaluation criteria For starch (porridge) stains, an iodine solution was applied to the bowl after washing; for oil (beef tallow) stains, an oil red solution was applied to the porcelain plate after washing; and for protein (egg yolk) stains, the degree of stain removal was evaluated visually as follows. ◎: Removes over 90% of dirt. ○: Removes 70% or more of dirt but less than 90%. △: Removes 50% or more but less than 70% of dirt. ×: Removes less than 50% of dirt.

[0045] [Washing Test 4] To evaluate the cleaning performance when water hardness is high, the following tests and evaluations were conducted. • Test method A detergent composition prepared at 0.20% concentration using artificial hard water was evaluated for its cleaning performance using the Leenatz test method (JIS K 3362:2008). The materials to be cleaned were prepared by coating 76mm x 26mm microscope slides with three types of stains: starch (porridge), fat (beef tallow), and protein (egg yolk), and drying them for 24 hours. Three microscope slides with each type of stain were treated as a set and cleaned under the following cleaning conditions, and their cleanability was evaluated according to the following evaluation criteria. *Cleaning conditions Detergent concentration: 0.20% Washing temperature: 45℃ Washing time: 10 minutes Hardness of the artificial hard water used: (as CaCO3) 150 ppm Starch (porridge) stains: 40g of cooked rice was placed in 400g of hot water, boiled at 90-100°C for 20 minutes, and the supernatant was applied to a microscope slide at a rate of 0.01g per slide. The slides were dried at room temperature for 30 minutes, and immediately before washing, they were immersed in 40°C water for 10 minutes. Fat (beef tallow) stains: 20g of fat (beef tallow and soybean oil mixed in a 1:1 volume ratio), 0.25g of monoolein, and 0.1g of oil red were dissolved in 60mL of chloroform, and this solution was applied to a microscope slide at a rate of 0.02g / slide. Protein (egg yolk) stains: Egg yolk from chicken eggs was attached to a glass slide at a rate of 0.2g per slide, dried at room temperature for 1 hour, and then immersed in 40°C water for 30 minutes immediately before washing. • Evaluation criteria For starch (porridge) stains, an iodine solution was applied to the bowls after washing. For oil (beef tallow) and protein (egg yolk) stains, the degree of stain removal was evaluated visually according to the following criteria. ◎: Removes over 90% of dirt. ○: Removes 70% or more of dirt but less than 90%. △: Removes 50% or more but less than 70% of dirt. ×: Removes less than 50% of dirt.

[0046] [Storage stability] • Test method The prepared cleaning agent composition was placed in a 100 mL glass bottle and stored in a constant temperature bath (SLI-4S, manufactured by Sunaka Rika Kogyo Co., Ltd.) at 40°C, and simultaneously in an incubator (MTH-2400, manufactured by Sanyo Corporation) under a programmed temperature control of -5°C to 5°C. The bottle was stored in this condition for one month. Its appearance was then visually observed and evaluated according to the following evaluation criteria. • Evaluation criteria ◎: After one month, there were absolutely no changes in appearance such as turbidity, separation, or precipitation. ○: After one month, slight changes in appearance such as turbidity, separation, and precipitation were observed. △: After two weeks, slight changes in appearance such as turbidity, separation, or precipitation were observed. ×: Immediately after adjustment, there were changes in appearance such as turbidity, separation, or precipitation.

[0047] [Enzyme activity stability] • Test method For α-amylase and protease, the enzyme activity values ​​in the detergent composition after 2 weeks at 40°C were determined. For lipase and cellulase, the remaining percentage was calculated from the enzyme activity values ​​in the detergent composition after 4 weeks at room temperature (around 23°C), and evaluated as follows. However, the above enzyme activity values ​​were determined as follows. *How to determine α-amylase activity levels A tablet containing an indicator that changes color upon decomposition of starch, along with starch (Fadebas tablet), was added to an aqueous solution of a detergent, and the concentration of the pigment was measured. * How to determine protease activity levels A detergent aqueous solution and a casein solution were mixed, trichloroacetic acid solution was added, and then the Folin-Ciocalten reagent was added dropwise, and the color development of the solution was measured. * How to determine lipase activity levels An emulsified olive oil solution was prepared, and after adding an aqueous solution of a detergent and stirring, a few drops of phenolphthalein indicator were added, and the solution was titrated with sodium hydroxide solution. • Evaluation criteria ◎: Survival rate 70% or more. ○: Survival rate of 40% or more but less than 70%. △: Survival rate between 25% and 40%. ×: Survival rate less than 25%.

[0048] [Low foaming] • Test method A detergent composition diluted with tap water and 30g of chicken eggs (whole eggs) thoroughly mixed were placed in a commercial automatic dishwasher (JWE-680UB-G, manufactured by Hoshizaki Corporation) and operated under the following operating conditions. The foaming of the washing solution was then visually evaluated according to the evaluation criteria described below. *Driving conditions Detergent concentration: 0.10% by mass Washing temperature: 40℃ Washing course: Standard washing cycle (Wash: 43 seconds, Rinse: 15 seconds) Tap water hardness: (as CaCO3) 50-60 mg / L • Evaluation criteria ◎: During operation, the foam is less than 50mm above the liquid surface, and the foam disappears quickly after operation ends. ○: During operation, the bubbles are less than 50 mm above the liquid surface, and the bubbles disappear within 1 minute after the end of operation. △: During operation, bubbles are 50mm or more above the liquid surface, but disappear within 1 minute after the end of operation. ×: Regardless of the foam height during operation, the foam remains even 1 minute after the end of operation.

[0049] [Re-deposition prevention] • Test method 30g of salad oil colored with oil red, along with the prepared detergent composition, was placed in a commercial automatic dishwasher (JWE-680UB-G, manufactured by Hoshizaki Corporation). The machine was operated under the following conditions, and the degree of dirt adhering to the melamine dish was visually inspected and evaluated based on the following evaluation criteria. *Driving conditions Detergent concentration: 0.2% by mass Washing temperature: 60℃ Rinse temperature: 80℃ Rinse water volume: 2.2L Washing course: Standard washing cycle (Wash: 50 seconds, Rinse: 10 seconds) Tap water hardness: (as CaCO3) 60 mg / L • Evaluation criteria ◎: There was absolutely no dirt on the cleaning dish. ○: There was almost no dirt attached to the cleaning tray. △: Dirt was found on the cleaning dish. ×: There was a considerable amount of dirt on the cleaning dish.

[0050] [pH: undiluted solution, 25℃] ·Measurement method Using a pH meter (pH METER F-12, manufactured by Horiba, Ltd.), the pH value of the undiluted detergent composition at 25°C was measured in accordance with JIS Z-8802:1984, and evaluated based on the following evaluation criteria. • Evaluation criteria ◎: 8.0 or higher and 10.0 or lower. ×: Less than 8.0 or greater than 10.0.

[0051] The details of the components shown in Tables 1-6 below are as follows, and unless otherwise specified, the values ​​in each table represent the effective concentration.

[0052] [Component A: Alkanolamine] • Alkanolamine 1: (Triethanolamine) Product name: Triethanolamine S, manufactured by Nippon Shokubai Co., Ltd. • Alkanolamine 2: (Monoethanolamine) Product name: Monoethanolamine, manufactured by Nippon Shokubai Co., Ltd.

[0053] [Component B: Polyelectrolyte polymer] (B1) ·Polyelectrolyte polymer 1: (Maleic acid polymer, average molecular weight 2,000, purity 50%) Product name: Non-Pole PMA-50W, manufactured by NOF Corporation (pH: 1) ·Polyelectrolyte polymer 2: (Acrylic acid / maleic acid copolymer, average molecular weight 3,000, purity 50%) Product name: Non-Pole PMA-50W, manufactured by NOF Corporation (pH 1.5) ·Polyelectrolyte polymer 3: (Polyacrylic acid, average molecular weight 4,500, purity 48%) Product name: Acusol 445, manufactured by Dow Chemical (pH 3.5) ·Polyelectrolyte polymer 4: (Polyacrylic acid, average molecular weight 10,000, purity 45%) Product name: Aqualic HL-415, manufactured by Nippon Shokubai Co., Ltd. (pH 2) ·Polyelectrolyte polymer 5: (Polyacrylic acid, average molecular weight 100,000, purity 35%) Product name: SokalanPA80S, manufactured by BASF (pH2) (B2) ·Polyelectrolyte polymer 6: (Sodium polyacrylate, average molecular weight 3,500, purity 44%) Product name: Aqualic DL-40S, manufactured by Nippon Shokubai Co., Ltd. ·Polyelectrolyte polymer 7: (Na salt of acrylic acid-sulfonic acid copolymer, average molecular weight 3,000, purity 50%) Product name: Aqualic GL-246, manufactured by Nippon Shokubai Co., Ltd. ·Polyelectrolyte polymer 8: (Na salt of acrylic acid-maleic acid copolymer, average molecular weight 60,000, purity 40%) Product name: Aqualic TL-200, manufactured by Nippon Shokubai Co., Ltd. ·Polyelectrolyte polymer 9: (Na salt of olefin-maleic acid copolymer, average molecular weight 12,000, purity 25%) Product name: SokalanCP9, manufactured by BASF

[0054] [Component C: Nonionic surfactant] (C1) • Nonionic surfactant 1: (Polyoxyethylene alkyl ether, 1% by mass aqueous solution, cloud point 17°C) Product name: Sedran SF-506, manufactured by Sanyo Chemical Industries, Ltd. (C2) Nonionic surfactant 2: (A mixture of polyoxyalkylene alkyl ether and polyalkylene glycol, with a cloud point of 18°C ​​in a 1% by mass aqueous solution.) Product Name: Dowfax DF-147Defoamer, manufactured by Dow Chemical Corporation • Nonionic surfactant 3: (A mixture of polyoxyalkylene alkyl ether and polyalkylene glycol, with a cloud point of 33°C in a 1% by mass aqueous solution.) Product name: Neugen LF-202N, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (C3) • Nonionic surfactant 4: (Polyoxyalkylene branched decyl ether, 1% by mass aqueous solution, cloud point 20°C) Product name: Neugen LF-40X, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Nonionic surfactants other than C1, C2, and C3) • Nonionic surfactant 5: (Polyoxyethylene polyoxypropylene block polymer (pull-lock type block polymer), cloud point 60°C in 1% by mass aqueous solution) Product name: Epan 740, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. • Nonionic surfactant 6: (Polyoxyethylene polyoxypropylene block polymer (reverse pluronic type block polymer), cloud point 50°C in 1% by mass aqueous solution) Product name: Pluronic® RPE1740, manufactured by BASF.

[0055] [Component D: Enzyme] • Enzyme 1: (α-amylase) Product name: Stainzyme Plus 12L, manufactured by Novozymes Japan. • Enzyme 2: (α-amylase) Product name: Achieve Alpha100L, manufactured by Novozymes Japan. • Enzyme 3: (Protease) Product Name: PROGRESS UNO 100L, manufactured by Novozymes Japan Co., Ltd. • Enzyme 4: (Lipase) Product name: LIPEX 100L, manufactured by Novozymes Japan Co., Ltd.

[0056] [Component E: Solubilizer] • Solubilizer 1: (Sodium cumenesulfonate, active ingredient amount 40%) Product name: Teika Tox N5040, manufactured by Teika Corporation • Solubilizer 2: (Hexyl glucoside, active ingredient amount 75%) Product name: AG6206, manufactured by Lion Specialty Chemicals. • Solubilizer 3: (Decyl glucoside, active ingredient amount 65%) Product Name: ALKYL POLYGLYCOSIDES APG0810 65%, manufactured by Azelis Japan Co., Ltd.

[0057] [Other ingredients] Stabilizer (Calcium chloride, as anhydrous, 74.3%) Product Name: Calcium Chloride Granules, manufactured by Central Glass Co., Ltd. • Water-soluble solvents (Glycerin, active ingredient amount 99%) Product name: Food additive glycerin, manufactured by Miyoshi Oil & Fat Co., Ltd. Chelatives (Citrate monohydrate, active ingredient content 91%) Product name: Purified citric acid (crystalline), manufactured by Fuso Chemical Industry Co., Ltd. [Component F: Water] Ion-exchanged water

[0058] [Table 1]

[0059] [Table 2]

[0060] [Table 3]

[0061] [Table 4]

[0062] [Table 5]

[0063] [Table 6]

[0064] From the results above, it can be seen that Examples 1 to 23 generally received excellent evaluations for all evaluation items. On the other hand, Comparative Examples 1 to 12, which fall outside the scope defined in the present invention, received an "X" rating, indicating that there are problems with one or more of the following: washing test 1, washing test 2, washing test 3, washing test 4, storage stability, enzyme activity stability, low foaming, or anti-re-adhesion properties. Furthermore, among the examples, those with a high content of (A) tend to show improved cleansing properties against proteins. However, even if the content of (A) is high, if the content of (B1) is also high, (A) acts as a neutralizing agent, and the cleansing properties against proteins tend to decrease. [Industrial applicability]

[0065] The liquid cleaning agent composition for hard surfaces of the present invention provides sufficient cleaning performance and re-adhesion prevention against starch, oil, and protein stains, even when the water used for cleaning has high hardness, and exhibits excellent system stability of the cleaning composition, making it highly promising.

Claims

1. A liquid cleaning agent composition for hard surfaces containing (A) an alkanolamine, (B) a polymer electrolyte, (C) a nonionic surfactant, (D) an enzyme, (E) a solubilizer, and (F) water, The (B) polymer electrolyte polymer contains the following (B1) and (B2), the content of (B1) and (B2) is set to the following ranges with respect to the entire hard surface liquid cleaning agent composition, and the mass ratio of (B1) to (B2) (B1 / B2) is set to 0.1 to 6 in the hard surface liquid cleaning agent composition. (B1) A polyelectrolyte polymer having a carboxyl group and a mass-average molecular weight of 1,000 to 500,000, with a pH of 4 or less at 25°C: 0.5 to 5% by mass. (B2) Potassium salt and / or sodium salt of a polyelectrolyte polymer having a carboxyl group and a mass-average molecular weight of 1,000 to 100,000: 0.5 to 5% by mass.

2. The liquid cleaning agent composition for hard surfaces according to claim 1, wherein the (C) nonionic surfactant comprises at least one selected from the group consisting of (C1), (C2), and (C3) below, the content of (C1), (C2), and (C3) is set to the following ranges with respect to the entire liquid cleaning agent composition for hard surfaces, and the sum of (C1), (C2), and (C3) is 1 to 10% by mass of the entire liquid cleaning agent composition for hard surfaces. (C1) A nonionic surfactant consisting of a polyoxyalkylene alkyl ether, having a cloud point of 35°C or less in a 1% by mass aqueous solution: 5% by mass or less. (C2) A nonionic surfactant consisting of a mixture of polyoxyalkylene alkyl ether and polyalkylene glycol, having a cloud point of 35°C or less in a 1% by mass aqueous solution: 5% by mass or less. (C3) A nonionic surfactant consisting of polyoxyethylene polyoxypropylene decyl ether, having a cloud point of 35°C or less in a 1% by mass aqueous solution: 10% by mass or less.

3. A liquid cleaning agent composition for hard surfaces according to claim 1 or 2, wherein the pH at 25°C is set in the range of 8.0 to 10.

0.

4. A liquid cleaning agent composition for hard surfaces according to claim 1 or 2, wherein it does not contain a chelating agent, or if it does, the amount of the chelating agent is 1% by mass or less.

Images